Lubricants comprising novel cyclopentanes, cyclopentadienes, cyclopentenes, and mixtures thereof and methods of manufacture

ABSTRACT

Hydrocarbyl substituted cyclopentadienes, cyclopentenes, and cyclopentanes are sythetic lubricating compositions. The preferred structures contain 1 to 6 alkyl groups which have 4 to 36 carbon atoms and may have different and varying carbon chain structures. The cyclopentenes and cyclopentanes are prepared by hydrogenation from the corresponding cyclopentadiene intermediates. The cyclopentadienes are prepared by reaction with hydrocarbylating agents or alcohols. Mixtures are also disclosed.

FIELD OF THE INVENTION

This invention relates to novel hydrocarbyl-substituted cyclopentanes,hydrocarbyl-substituted cyclopentadienes, hydrocarbyl-substitutedcyclopentenes, and mixtures thereof, and their use as lubricatingcompositions, and more particularly, this invention relates to novelhydrocarbyl cyclopentanes, hydrocarbyl cyclopentadienes, hydrocarbylcyclopentenes, and mixtures thereof, novel methods for formation of thecyclopentadienes and their conversion to the cyclopentenes andcyclopentanes, and use of the cyclopentanes, cyclopentadienes,cyclopentenes and mixtures thereof as lubricating compositions.

BACKGROUND

Cyclopentadiene, cyclopentene and cyclopentane and alkylated derivativesthereof are known in the art. Further, methods are known for preparationof alkylated cyclopentadienes and conversion of these materials tocyclopentenes and cyclopentanes. There is substantial interest incyclopentadienes, cyclopentenes, and cyclopentanes since cyclopentadieneis characterized by the unique property of being the most acidicaliphatic hydrocarbon known, having a pKa of 18, and also because itsreactions as a Diels-Alder diene are extremely facile. Because of thearomaticity of the cyclopentadiene anion (c--C₅ H₅ ⁻), cyclopentadieneis easily the most acidic of the simple hydrocarbons and in fact iscomparable in acidity to alcohols. This means that substantial amountsof the anion can be generated with alkoxides and even concentratedsolutions of hydroxide. Since it it uniquely stable, it can participatein the carbanion reactions of alkylation, acylation, carboxylation andthe like.

U.S. Pat. No. 3,255,267 to Fritz et al relates to the alkylation ofcyclopentadienes and discloses the reaction of 1-alkyl or 2-alkylcyclopentadienes with a primary or secondary alcohol in the presence ofan alkaline catalyst to alkylate in either the 1 to 2 position. The 1isomer may then be further alkylated in either the 3 or 4 position whilethe 2 isomer can be further alkylated in the 4 position, all of thisresulting in the formation of a mixture of isomers. Trialkylated andtetralkylated products are also disclosed. The compounds are describedas being capable of epoxidation, polymerization, or for use asintermediates for preparation of other compounds. The alkyl groups addedto the cyclopentadiene structure are inclusive of alkyl radicals having1 to 11 carbon atoms in n-alkyl chains and up to 21 carbon atoms in sidechains when the compounds are formed from secondary alcohols andincluding up to four alkyl substituents on the said cyclopentadiene.

U.S. Pat. No. 3,560,583 discloses cyclopentadiene compounds containingup to five substituents, which substituents can be independentlyhydrogen, alkyl, aryl or aralkyl. These compounds are prepared byreaction of a cyclopentadiene compound with benzyl halide or allylhalide, an alkali metal hydroxide and a quaternary ammonium saltcatalyst.

Polish Pat. No. 55,535 to Makosza, 1968, discloses indene compoundswhich contain alkyl substituents on the cyclopentadiene portion of themolecule. However, the working examples indicate that only a singlealkyl group or two allyl groups are present. U.S. Pat. No. 3,931,334discloses lubricant compositions which comprise substituted indans, theindan molecule being substituted by methyl and styryl.

In a thesis by Stephen S. Hirsch, University of Maryland, 1963, there isdisclosure of base catalyzed alkylation of cyclopentadienes utilizingalcohols to effect the alkylation. Included in this disclosure arealkylation reactions with benzyl alcohol to produce cyclopentadieneswhich can contain as many as five benzyl substituents. Also disclosedare 1,3-dialkyl indenes.

Polish Pat. No. 55,571 to Makosza discloses cyclopentadienes andprocesses for preparation of monosubstituted cyclopentadienes by the useof phase-transfer alkylation. The patent is limited to monosubstitutedcompounds with short chain alkyl groups.

The prior art contains numerous disclosures of methods for thepreparation of substituted cyclopentadienes but wherein the substituentsusually are short chain alkyl groups. The methods of preparation of suchmaterials vary but do include such processes as the reaction of thecyclopentadiene with alkyl halides in the presence of a base as in U.S.Pat. No. 2,953,607. Similar disclosures may be found in U.S. Pat. Nos.3,131,227, 4,547,603, 4,567,308, 3,560,583, 4,412,088, and 3,755,492. Ofparticular interest is 3,131,227 which discloses polysubstitutedcyclopentadienes such as pentamethyl and hexamethyl cyclopentadienewhich is prepared by a cyclization reaction. Also in Pat. No. 4,567,308,alkyl cyclopentadienes and alkylated derivatives thereof are prepared bythe vapor phase reaction of a cyclopentadiene derivative and analiphatic lower alcohol in the presence of a basic catalyst. Thesecyclopentadienes and alkylated products are disclosed as being additivesfor synthetic rubbers, starting materials for resins and/or industrialchemicals.

In a publication by J. Denis, Journal of Synthetic Lubrication, Vol. 1,p. 201-219 (1985), there is disclosure of hydrocarbons which may be usedin lubricant compositions. Specifically mentioned in this publicationare cycloalkanes and in particular monoalkyl substituted cyclopentanes.This publication is a comparison of various hydrocarbon structuresincluding normal alkanes, alkanes branched by one or more alkyl chainsor by a ring, cycloalkanes and aromatics as base stocks for lubricants.

In a publication by Rong et al, Acta Chemica Sinica, Vol. 41, No. 10,October, 1983, pages 971-973 there is disclosure of the use ofpolyethylene glycol as a phase transfer agent for halide alkylation ofcyclopentadiene with alkyl halides. The products produced are monoalkylsubstituted cyclopentadienes. In a related article by Rong et al,Journal of Chinese Universities, Vol. 4, page 576-580 (1983), there isdisclosure of the synthesis of alkyl substituted derivatives ofcyclopentadiene by the phase transfer catalytic reaction ofcyclopentadiene with alkyl halides in the presence of potassiumhydroxide and polyoxyethylene surfactants as a catalyst. Only monoalkylsubstituted cyclopentadienes are prepared.

U.S. Pat. Nos. 3,004,384, 3,356,704, 3,358,008, 3,388,180, 3,391,209,3,414,626, and 3,419,622 disclose polysubstituted cyclopentadienes andcyclopentanes but wherein the substituent is a short chain alkyl groupgroup or allyl group. Finally, U.S. Pat. Nos. 3,751,500 and 3,636,176disclose indene compounds which can contain short chain alkylsubstituents which are useful as perfume compositions.

In none of the prior art of which Applicants are aware are theredisclosures of poly-hydrocarbyl cyclopentanes, cyclopentadienes,cyclopentenes, and mixtures thereof which are useful as lubricantcompositions, which useful products may be prepared from novelhydrocarbyl-substituted cyclopentadienes. The present invention providessuch novel products as well as methods for their preparation and methodsfor their use.

SUMMARY OF THE INVENTION

It is accordingly one object of the present invention to providehydrocarbon-substituted cyclopentanes which are useful as lubricatingcompositions.

A further object of the invention is to provide novel and usefulcyclopentanes which are polyhydrocarbyl substituted and which areprepared from the corresponding hydrocarbyl substitutedcyclopentadienes.

A still further object of the present invention is to providelubricating compositions which contain hydrocarbyl-cyclopentanes as alubricating component.

There are also provided novel intermediate compositions of matter whichcomprise hydrocarbyl-substituted cyclopentadienes andhydrocarbyl-substituted cyclopentenes, the cyclopentadienes andcyclopentenes also being useful as lubricating compositions.

Also provided by the present invention are lubricating compositionswhich comprise novel poly-hydrocarbyl substituted cyclopentadienes andpolyhydrocarbyl substituted cyclopentenes.

Also provided by the present invention are lubricating compositionscomprising mixtures of hydrocarbyl cyclopentanes, hydrocarbylcyclopentenes, and/or hydrocarbyl substituted cyclopentadienes,optinally in admixture with a natural lubricant such as mineral oil orother synthetic lubricants as base fluids.

Further provided by the present invention are novel methods forpreparation of the hydrocarbon-substituted cyclopentadienes comprising aphase transfer method and an alcohol method.

Other objects and advantages of the present invention will becomeapparent as the description thereof proceeds.

In satisfaction of the foregoing objects and advantages of the presentinvention, there is provided as a broad embodiment of the invention, aclass of lubricating compositions which comprise one or morehydrocarbyl-substituted cyclopentanes. These hydrocarbyl-substitutedcyclopentanes include the individual compounds and mixtures of thehydrocarbyl-substituted cyclopentane compounds. The compounds are of thefollowing general formula: ##STR1## wherein in the above formula, eachR₁ is individually and independently selected from alkyl groups of 1 to4 carbons, each R₂ is individually and independently selected fromhydrocarbyl groups containing about 4 to 36 carbon atoms, z is 0, 1, 2or 3, and x is an integer ranging from 1 to 6, and x+z cannot be greaterthan 6. Preferred compounds within this group are those wherein each R₂is individually and independently selected from alkyl groups havingabout 8 to 24 carbon atoms, x is an integer of about 2 to 5, and thetotal number of carbon atoms in the R₂ groups should preferably notexceed about 80.

In a further embodiment of the invention, there are provided novelcyclopentane compositions which are useful as lubricating compositionsand which are of the following general formula: ##STR2## wherein each R₁is individually and independently selected from alkyl groups of 1 to 4carbons, each R₂ is individually and independently selected fromhydrocarbyl groups having about 4 to 36 carbon atoms, preferablystraight or branch chained alkyl groups, z is 0, 1, 2 or 3 and y is aninteger ranging from 2 to 6, provided that when at least 2 of the R₂substituents contain alkyl groups of from 4 to 10 carbon atoms, then ymust be an integer of at least 3, y+z cannot be greater than 6. Thetotal number of carbon atoms in the R₂ groups should preferably notexceed about 80.

There are further provided by the present invention novelcyclopentadiene intermediate compounds which can be hydrogenated to thecyclopentanes referred to above, which intermediate cyclopentadienes areof the following general formula: ##STR3## wherein in the above formula,each R₁ is individually and independently selected from alkyl groups of1 to 4 carbon atoms, each R₂ is individually and independently selectedfrom hydrocarbyl groups, preferably straight or branch chained alkyl oralkenyl groups of 4 to 36 carbon atoms, z is 0, 1, 2 or 3, and y is aninteger of from 2 to 6, and y+z cannot be greater than 6, provided thatwhen up to four of the R₂ groups contain from 4 to 11 carbon atoms, theny must be an integer of at least 5. The total number of carbon atoms inthe R₂ groups should preferably not exceed about 80.

The cyclopentadiene compounds of the above formula, referred to as novelintermediate compounds, are also included in a group of novellubricating compositions. Thus, polyhydrocarbyl substitutedcyclopentadienes of the following formula are useful as lubricatingcompositions: ##STR4## wherein in the above formula, each R₁ isindividually and independently selected from alkyl groups of 1 to 4carbon atoms, each R₂ is individually and independently selected fromhydrocarbyl groups containing about 4 to 36 carbon atoms, z is 0, 1, 2or 3, and x is an integer ranging from about 1 to 6, and x+z cannot begreater than 6. Preferred compounds within this group are those whereineach R₂ is individually and independently selected from alkyl or alkenylgroups having about 8 to 24 carbon atoms and x is an integer of about 2to 5, and the total number of carbon atoms in the R₂ groups shouldpreferably not exceed about 80. The cyclopentadienes of this formula mayalso be used as intermediates for hydrogenation to the cyclopentene andcyclopentane lubricants of the invention.

There are also provided by the present invention lubricatingcompositions which are partially synthetic lubricants and partiallynatural lubricants. These lubricating compositions comprise thehydrocarbyl substituted cyclopentanes, or the hydrocarbyl substitutedcyclopentadienes, or the hydrocarbyl substituted cyclopentenes, or anymixture thereof, in any proportions with a natural lubricant base suchas mineral oil. Also provided are mixtures of the synthetic lubricatingcompositions of the present invention with other synthetic lubricants sothat the resulting lubricating composition is a mixture of syntheticlubricants. Also included within the scope of the invention are mixturesof any or all of the synthetic lubricants of the present invention,alone or in admixture with other synthetic lubricants, or with naturallubricants.

Also provided by the present invention are methods for production of thehydrocarbyl-substituted cyclopentadiene compounds, one method comprisingthe single step reaction of cyclopentadiene or substitutedcyclopentadiene with a molar excess of a hydrocarbylating agent ormixture of such agents of the formula R₂ Y, wherein R₂ is as describedabove and Y is a leaving group, preferably a halogen, in a reactionvessel containing an aqueous alkaline solution and a phase transfercatalytic agent. In a second method for preparation of the novelcyclopentadienes, cyclopentadiene or substituted cyclopentadiene isreacted with a molar excess of a primary or secondary alcohol or mixtureof such alcohols of the formula R₂ OH wherein R₂ is as described abovein the presence of a basic catalyst at elevated temperatures, and withremoval of water as it is formed, and recovering the product.

DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention is broadly concerned with lubricating compositionswhich comprise certain hydrocarbyl cyclopentanes, hydrocarbylcyclopentadienes, hydrocarbyl cyclopentenes, or mixtures thereof, andmethods of preparation. The invention is also concerned with a class ofnovel cyclopentanes and corresponding cyclopentadiene and cyclopenteneintermediates, methods for their preparation and methods for conversionof the cyclopentadienes to the cyclopentane lubricants.

In a main embodiment of the invention, novel synthetic fluids which arelubricating compositions comprise a group of polyhydrocarbyl-substitutedcyclopentanes of the following formula: ##STR5## wherein in the aboveformula, each R₁ is individually and independently selected from alkylgroups of 1 to 4 carbon atoms, each R₂ is individually and independentlyselected from hydrocarbyl groups containing from about 4 to about 36carbon atoms and preferably is a straight or branch chained alkyl groupof 4 to 36 carbon atoms, z is 0, 1, 2 or 3, and x is an integer rangingfrom 2 to 6, and x+z cannot be greater than 6.

It will be understood that in Formula I as well as in Formulae II toVIII described hereinafter, that the R₂ hydrocarbon groups can bestraight or branch-chained, can be of the same or different chainlength, and can contain alicyclic rings of 3 to 7 carbon atoms. Sincethe cyclopentanes are produced by hydrogenation, little if anyunsaturation, except possibly for aromatic double bonds, will remain inthe hydrocarbon substituents. In the definition of R₁ in the Formula Icompounds, as well as the compounds of Formulae II to VIII describedhereinafter, it will be understood that the alkyl groups may be the sameor different and straight or branch-chained.

These hydrocarbon substituted cyclopentanes have been found to provideexcellent lubricating characteristics which make them useful aslubricants in internal combustion engines and in other areas where goodlubricity is a requirement. The lubricants may comprise individualhydrocarbyl-substituted cyclopentanes or mixtures thereof. The compoundsprovide the appropriate specific gravity, refractive indicies,viscosities, and low and high temperature characteristics which arerequired for an outstanding lubricant. In particular the lubricantsexhibit specific gravities ranging from about 0.835 to about 0.860;refractive indices ranging from about n_(D) ²⁵ C 1.450 to 1.40;viscosities at 100° C. (cSt) ranging from 2.0 to 20.0, at 40° C. (cST)ranging from 6.0 to 350, at 0° C. (cP) ranging from 200 to 13,000, andat -40° C. (cP), ranging from 1500 to 600,000. The viscosity indexranges from 45 to 200. The compositions also provide excellent lowtemperature pour points. Flash points range from 500° to 600° F. andfire points range from 500 to 650 with minimum loss to evaporation atthese temperatures.

In the hydrocarbon substituted cyclopentane compositions describedabove, some compounds of the above formula which contain a single methylgroup substituent provide lubricants which have a lowered pour point ascompared to otherwise comparable cyclopentanes. This causes thecyclopentanes to be particularly useful in certain lubricatingenvironments.

A preferred group of hydrocarbon substituted cyclopentane lubricants arethose wherein x is an integer of 3 to 5, R₁ is methyl and z is 0 or 1,and R₂ is an alkyl group of 8 to 24 carbon atoms, and wherein x is aninteger of 2 to 4, R₁ is methyl and z is 0 or 1, and R₂ is an alkylgroup of 13 to 24 carbon atoms.

In further embodiments of the invention, the intermediatehydrocarbon-substituted cyclopentadienes and hydrocarbon substitutedcyclopentenes are also provided as lubricating compositions. Thesecompounds have lubricating characteristics including viscosities andpour points which make them useful in a variety of areas.

The lubricating compositions which comprise cyclopentadienes are of thefollowing formula: ##STR6## wherein z, R₁ and R₂ are as defined above inFormula I and x is an integer ranging from 1 to 6.

Also provided by the present invention are cyclopentene compositionswhich are useful as synthetic lubricants. These cyclopentenes may bedescribed by the following general formula: ##STR7## wherein R₁, R₂, zand and x are as defined above.

There is also provided by the present invention partial syntheticlubricant compositions in which the hydrocarbon-substitutedcyclopentanes, the hydrocarbon-substituted cyclopentenes, or thehydrocarbon-substituted cyclopentadienes, used either alone or inadmixture, are mixed with a natural base fluid such as mineral oil toform the lubricant. Compositions of this type may contain about 10 to90% of any of the synthetic lubricants of this invention mixed with 90to 10% of a mineral oil base fluid. Compositions of this type showenhanced lubricant properties.

In a further embodiment of the invention, mixtures of thehydrocarbon-substituted cyclopentanes, the hydrocarbon-substitutedcyclopentenes, or the hydrocarbon-substituted cyclopentadienes, usedeither alone or in admixture, may be mixed with other syntheticlubricants such as poly-alpha-olefins, esters and polyol esters. Thesemixtures may include 10 to 90% of the synthetic hydrocarbon substitutedcyclopentanes, cyclopentenes, and/or cyclopentadienes of this invention,mixed with 90 to 10% of any other compatible synthetic lubricant.

In a still further embodiment of the invention, lubricating compositionsare provided which comprise mixtures of the hydrocarbon-substitutedcyclopentanes, hydrocarbon-substituted cyclopentenes, andhydrocarbon-substituted cyclopentadienes of this invention, the mixturesbeing in varying and all proportions. Mixtures of this type arise fromincomplete hydrogenation in production of the cyclopentanes from thecyclopentadienes as described hereinafter. This hydrogenated mixturewill comprise mixtures of these compounds which can be used as such as alubricating composition.

Preferred lubricating compositions according to the invention are thosecyclopentanes, cyclopentenes and cyclopentadienes which contain aplurality of R₂ hydrocarbyl groups, i.e., wherein x is 3 to 6. Even morepreferred are those compounds wherein the R₂ substituents arehydrocarbyl groups of different carbon chain length.

In a further embodiment of the invention, there are also provided agroup of novel hydrocarbyl substituted cyclopentanes which are of thefollowing formula: ##STR8## wherein in the above formula, R₁ isindividually and independently selected from alkyl groups of 1 to 4carbon atoms, R₂ is individually and independently selected fromhydrocarbyl groups of 4 to 36 carbon atoms, and preferably are straightor branch chained alkyl groups containing 4 to 36 carbon atoms which cancontain alicyclic rings of 3 to 7 carbon atoms, z is 0, 1, 2 or 3, and yis an integer of from 2 to 6, provided that when at least two of the R₂groups are carbon chains of from about 4 to 10 carbon atoms, then theinteger y must be at least 3, and y+z cannot be greater than 6.

The hydrocarbon-substituted cyclopentanes of the present invention areprepared by hydrogenation of the corresponding hydrocarbon-substitutedcyclopentadienes by conventional hydrogenation techniques. Thehydrogenation reactions of this type are known in the art and generallycomprise reaction of the hydrocarbon-substituted cyclopentadieneintermediate or mixture of intermediates in the presence of ahydrogenation catalyst such as Raney nickel or palladium and in thepresence or absence of an organic solvent such as an aliphatichydrocarbon. In carrying out the hydrogenation reaction, the reactor ispressurized with hydrogen to a pressure which may range up to about 3000psi and heated in the range of 75° to 200° C. until the hydrogenation iscomplete as evidenced by cessation of hydrogen uptake. On removal of thecatalyst and solvent, the hydrogenated cyclopentane is recovered.

The hydrocarbon-substituted cyclopentadienes which serve as precursors,many of which are also novel compounds, may be characterized by thefollowing general formula: ##STR9## In the above formula, R₁ isindividually and independently selected from alkyl groups of 1 to 4carbon atoms, R₂ is individually and independently selected fromhydrocarbon substituents of 4 to 36 carbon atoms, preferably straight orbranch-chained alkyl groups, alkenyl groups, or alkynyl groups havingfrom 4 to 36 carbon atoms which can contain alicyclic rings of 3 to 7carbons and/or aromatic rings of 6 to 12 carbon atoms, z is 0, 1, 2, or3, x+z cannot be greater than 6, and x is an integer ranging from 1 to6. It is preferred that at least two of the R₂ groups contain from 8 to13 carbon atoms, and that x be an integer of 3 to 5.

A novel group of cyclopentadiene compounds are those of the formula:##STR10## wherein z, R₁ and R₂ are as defined above, and y is an integerof 2 to 6, and y+z cannot be greater than 6, provided that when up tofour of the R₂ groups contain from 4 to 11 carbon atoms, then y is aninteger of at least 5.

The intermediate hydrocarbon-substituted cyclopentenes, most of whichare also novel compounds, may be characterized by the following generalformula: ##STR11## In the above formula, R₁ is individually andindependently selected from alkyl groups of 1 to 4 carbon atoms, R₂ isindividually and independently selected from hydrocarbon substituents of4 to 36 carbon atoms, preferably straight or branch-chained alkyl groupshaving from 4 to 36 carbon atoms which can contain alicyclic rings of 3to 7 carbons and/or aromatic rings of 6 to 12 carbons, z is 0, 1, 2 or3, and x is an integer ranging from 1 to 6, and x+z cannot be greaterthan 6. It is preferred that at least two of the R₂ groups contain from4 to 10 carbon atoms, and that x be an integer of 3 to 5. A preferredgroup of compounds includes those wherein the R₂ groups contain from 8to 12 carbon atoms and x is 3 to 5.

A novel group of cyclopentene compounds are those of the formula:##STR12## wherein z, R₁ and R₂ are as defined above, and y is an integerof 2 to 6, provided that when at least two of the R₂ groups contain from4 to 10 carbon atoms then y is an integer of at least 3. In aparticularly preferred group, when R₂ is an alkyl group which containsfrom 4 to 10 carbon atoms, then the integer x is 3, 4 or 5, the latterparticularly representing a group of novel cyclopentene intermediates.

In the cyclopentanes, cyclopentenes and cyclopentadienes of theinvention, the total number of carbon atoms in the R₂ substituentsshould preferably not exceed about 80.

Preferred compounds or mixtures of compounds according to the inventioninclude cyclopentane, cyclopentadiene, and cyclopentene lubricantswhich, with reference to Formulae I, II, and III, may be defined asfollows:

(1)

z=0;

x=3 or 4;

R₂ =C₈ and/or C₁₀ alkyl hydrocarbon.

(2)

z=0;

x=3 or 4;

R₂ =C₉ and/or C₁₀ and/or C₁₁ alkyl hydrocarbon.

(3)

z=0;

x=3 or 4; `R₂ =C₁₂ and/or C₁₃ alkyl hydrocarbon.

(4)

z=0;

x=2 or 3;

R₂ =2-octyl-1-dodecyl

Particularly preferred specific classes of compounds and specificcompounds or mixtures which are also useful as lubricants include thefollowing:

Cyclopentanes

Tri-n-octyl cyclopentane

Tetra-n-octyl cyclopentane

Penta-n-octyl cyclopentane

Tri-n-nonyl cyclopentane

Tetra-n-nonyl cyclopentane

Penta-n-nonyl cyclopentane

Tri-n-decyl cyclopentane

Tetra-n-decyl cyclopentane

Penta-n-decyl cyclopentane

Tri-n-undecyl cyclopentane

Tetra-n-undecyl cyclopentane

Penta-n-undecyl cyclopentane

Tri-n-dodecyl cyclopentane

Tetra-n-dodecyl cyclopentane

Penta-n-dodecyl cyclopentane

Tri-2-ethylhexyl cyclopentane

Tetra-2-ethylhexyl cyclopentane

Di-n-octyl, n-decyl cyclopentane

n-octyl, di-n-decyl cyclopentane

Trioctyl, n-decyl cyclopentane

Di-n-octyl, di-n-decyl cyclopentane

n-octyl, tri-n-decyl cyclopentane

Tri-n-tridecyl cyclopentane

Tetra-n-tridecyl cyclopentane

Penta-n-tridecyl cyclopentane

Cyclopentenes

Tri-n-octyl cyclopentene

Tetra-n-octyl cyclopentene

Penta-n-octyl cyclopentene

Tri-n-nonyl cyclopentene

Tetra-n-nonyl cyclopentene

Penta-n-nonyl cyclopentene

Tri-n-decyl cyclopentene

Tetra-n-decyl cyclopentene

Penta-n-decyl cyclopentene

Tri-n-undecyl cyclopentene

Tetra-n-undecyl cyclopentene

Penta-n-undecyl cyclopentene

Tri-n-dodecyl cyclopentene

Tetra-n-dodecyl cyclopentene

Penta-n-dodecyl cyclopentene

Tri-2-ethylhexyl cyclopentene

Tetra-2-ethylhexyl cyclopentene

Di-n-octyl, n-decyl cyclopentene

n-octyl, di-n-decyl cyclopentene

Trioctyl, n-decyl cyclopentene

Di-n-octyl, di-n-decyl cyclopentene

n-octyl, tri-n-decyl cyclopentene

Tri-n-tridecyl cyclopentene

Tetra-n-tridecyl cyclopentene

Penta-n-tridecyl cyclopentene

Cyclopentadienes

Tri-dodecyl cyclopentadiene

Tetra-dodecyl cyclopentadiene

Penta-dodecyl cyclopentadiene `Penta-n-butyl cyclopentadiene

Penta-n-octyl cyclopentadiene

Penta-n-nonyl cyclopentadiene

Penta-n-decyl cyclopentadiene

Di-n-octyl, n-decyl cyclopentadiene

n-octyl, di-n-decyl cyclopentadiene

Trioctyl, n-decyl cyclopentadiene

Di-n-octyl, di-n-decyl cyclopentadiene

n-octyl, tri-n-decyl cyclopentadiene

Tri-n-tridecyl cyclopentadiene

Tetra-n-tridecyl cyclopentadiene

Penta-n-tridecyl cyclopentadiene

The hydrocarbyl substituted cyclopentadiene intermediates of theinvention are prepared using a hydrocarbylating or phase transferpreparation method or an alcohol preparation method. In the phasetransfer method, cyclopentadiene or substituted cyclopentadiene and analkylating agent such as alkyl halide or mixture of alkyl halides areadded to a reaction vessel containing an alkaline aqueous solution andfurther containing a phase transfer catalytic agent. The alkylatingagent is used in a molar excess depending on the amount of alkylsubstitution desired. The preferred alkylating agent is an alkyl halideof the formula, R₂ Y wherein R₂ is as described above and Y is a leavinggroup, preferably Cl or Br, and the process is described herein withreference to this reaction. It is preferred that about 3 to 6 moles ofalkyl halide should be used per mole of cyclopentadiene. The alkalineaqueous solution will comprise sodium hydroxide or potassium hydroxidein preferred embodiments. The mixture of cyclopentadiene, alkyl halide,catalyst and alkali is permitted to react in aqueous solution withvigorous stirring for a period of from about 1/2 to 10 hours. Oncompletion of the reaction, and cessation of agitation, two phases willform, an organic phase and a water phase. The product will be containedin the organic phase and may be recovered by conventional methods as byseparation of phases and recovery.

It is sometimes desirable to add an organic solvent or water or both tofacilitate separation of the two phases. In a preferred procedure, theorganic layer is removed and any excess alkyl halide and/or solventremoved to provide the alkylated cyclopentadiene which can be used forconversion to the cyclopentane without further purification. This is asingle step reaction which provides good yields of the substitutedcyclopentadiene.

In conducting the hydrocarbylation reaction by the phase transfermethod, the preferred temperature range is from about -20° to 120° C.with a residence time or reaction time of from 1/2 hour up to 3 days.The molar ratio of alkyl halide to cyclopentadiene should range fromabout 1:1 up to about 20:1. The ratio of alkali metal hydroxide tocyclopentadiene reactant in this reaction may range from 1:1 up to 50:1.

Suitable phase transfer catalysts include n-alkyl (C₁₂ -C₁₆)dimethylbenzylammonium chloride, sold commercially as Hyamine 3500,triethylbenzylammonium chloride, sold commercially as TEBAC, a mixtureof methyl trialkyl (C₈ -C₁₀) ammonium chlorides, sold commercially asAdogen® 464, polyethylene glycols and polyethers.

In a separate method for preparation of the hydrocarbon-substitutedcyclopentadienes, an alcohol or mixture of alcohols of the formula R₂ OHwherein R₂ is as described above, is combined with a basic catalyst suchas an alkali metal hydroxide or alkoxide in a reaction vessel. Thealcohol reactant or mixture of alcohols is a primary or secondaryalcohol and is used in sufficient amounts to provide a molar excess ofabout 3 to 6 moles. The cyclopentadiene or hydrocarbon-substitutedcyclopentadiene is then added to the reaction vessel at room temperatureor a temperature as high as the reflux temperature of the mixture, whichwould be at about the boiling temperature of the alcohol(s) being used.Alternatively, a portion of the cyclopentadiene may be mixed with thealcohol and alkali in the reactor and the remaining cyclopentadieneadded to the reaction mixture over a period of time as the reactionproceeds. An inert solvent may also be included if necessary dependingon the alcohol reactants. Further, the reaction may be carried out in aclosed container so that higher temperatures in excess of 180°, and upto 260° C. can be reached using lower boiling alcohols. As the reactionproceeds, water will be produced and is removed as it is formed. Oncompletion of the reaction, the mixture is allowed to cool and thenmixed with water or poured onto ice and two layers allowed to separate.The organic and aqueous layers are separated using an organic solvent toaid the separation if necessary. After removal of excess alcohol and anysolvent from the organic layer, the polyalkyl cycopentadiene isrecovered.

In an alternative work-up procedure, the reaction mixture may befiltered. The alcohol may be separated by distillation before or afterfiltration.

It was unexpected that high yields of polyalkylated products fromalcohols, including long chain alcohols, could be obtained from thisreaction without the use of high pressure.

In conducting the hydrocarbylation by the alcohol method, minor sideproducts may be formed. For example, the acid corresponding to thealcohol and a dimeric alcohol may also be formed. The careful exclusionof oxygen and careful adjustment of the alcohol to base ratios aid insuppression of the formation of these byproducts. If secondary alcoholsare used, the byproducts are less significant.

The alcohol alkylation is preferably carried out in the temperaturerange of 180°-300° C. for a reaction time which may range from 10minutes to 3 days. The mole ratio of alcohol to cyclopentadiene mayrange from 1:1 up to 50:1 and the ratio of alkali metal hydroxide oralkoxide to cyclopentadiene reactant may range from 0.1:1 up to 10:1.

The precursor cyclopentadienes to be reacted by the phase transfermethod or alcohol method are preferably those set forth in Formula Vabove except that in such case, x can be 0, and x+z must be 0, 1, 2, 3,4 or 5 in the phase transfer method, and x+z must be 0, 1, 2, 3 or 4 inthe alcohol method. For example the R₁ and/or R₂ hydrocarbyl groupscould be added stepwise depending on the amount of hydrocarbylatingagent used. The final products and precursor compounds as described areconsidered to be inclusive of all such compounds.

The cyclopentene intermediates of this invention are produced by partialor incomplete hydrogenation of the cyclopentadienes when preparing thecyclopentanes. This hydrogenation reaction if carried to completion willproduce the cyclopentanes described above. However, incompletehydrogenation will result in production of at least some cyclopentenesand usually a mixture of the hydrocarbon substituted cyclopentenes andcyclopentanes. Some starting cyclopentadienes which are not hydrogenatedmay also remain in the mixture. Thus, the hydrogenation reaction canproduce a variety of mixtures of products as well as the cyclopentenesand the cyclopentanes of the invention.

The following examples are presented to illustrate the invention but theinvention is not to be considered as limited thereto. In the examplesand throughout the specification, parts are by weight unless otherwiseindicated.

EXAMPLE 1 Preparation of Di(n-octyl)cyclopentadienes (Phase TransferMethod)

Cyclopentadiene (99 g, 1.5 moles), and n-octyl bromide (476 g, 3.2moles), were added to a 5-liter reaction flask, containing an aqueous 56percent potassium hydroxide solution (1950 ml, 30 moles KOH) and acatalytic amount of Adogen® 464 (25 g), cooled in an ice bath. Themixture was stirred vigorously for 30 minutes in the ice bath, then thebath was removed. The mixture was stirred for an additional 3 hours,while warming to room temperature. The layers were separated, water andpentane being added to facilitate workup, and the organic phase waswashed with water until neutral. The organic layer was dried over MgSO₄and the pentane removed in vacuo, affording 372 g crude yield.

Gas chromatographic analysis provided the following analysis (86.5%total yield):

mono(n-octyl)cyclopentadienes 15.2%, 56.5 g, 0.317 moles (21.1% yield)

di(n-octyl)cyclopentadienes 75.7%, 281.6 g, 0.971 moles (64.7% yield);

tri(n-octyl)cyclopentadienes 1.1%, 4.1 g, 0.010 moles (0.6% yield).

EXAMPLE 2 Preparation of tri/tetra(n-decyl)cyclopentadienes (PhaseTransfer Method)

Cyclopentadiene (23 g, 0.35 moles), and n-decyl bromide (300 g, 1.36moles), were added to a 2-liter reaction flask containing an aqueous 56percent potassium hydroxide solution (500 ml, 7.5 moles KOH) and acatalytic amount of Adogen® 464 (13 g), in a water bath at roomtemperature. The mixture was vigorously stirred for one hour thenheated, with continuing stirring for 41/4 hours at 100° C. Aftercooling, the layers were separated, water and heptane added tofacilitate workup, and the organic phase was washed with water untilneutral. The organic phase was dried over MgSO₄ and the solvent removedin vacuo, affording 247 g crude yield. Unreacted n-decyl bromide (40 g,0.18 mole) was distilled off to give a pot residue (200 g) of product.

Gas chromatographic analysis provided the following analysis (98.6%total yield):

di(n-decyl)ether 3.4%, 6.8 g, 0.023 moles;

di(n-decyl)cyclopentadienes 0.8%, 1.6 g, 0.005 moles (1.4% yield);

tri(n-decyl)cyclopentadienes 41.2%, 82.4 g, 0.170 moles (48.6% yield);

tetra(n-decyl)cyclopentadienes 53.3%, 106.6 g, 0.170 moles (48.6%yield).

EXAMPLE 3 Preparation of Isodecylcyclopentanes (Alcohol method)

Isodecanol (420 g, 2.65 moles) and solid potassium hydroxide (87%, 10.3g, 0.16 moles KOH) were mixed in a 1-liter reaction flask fitted with amechanical stirrer, a dropping funnel, a Dean-Stark trap with condenser,a thermometer and a serum capped sampling port. Prior to heating, aportion of the dicyclopentadiene (6.6 g, 0.05 moles) was added to thereaction mixture. The flask was then heated to 200° C. After water begancollecting in the Dean-Stark trap, the remaining dicyclopentadiene (28.4g, 0.22 moles) was added dropwise over a 1.5 hour period. The reactionmixture was heated for 4 hours after the completion of thedicyclopentadiene addition. The temperature rose to 245° C. over thecourse of the reaction. After cooling, the reaction mixture was pouredinto water. Hexane was added to facilitate workup. The layers wereseparated. The aqueous layer was saved for further workup. The organicphase was washed with water until neutral. The organics were dried overMgSO₄ and the solvent removed in vacuo. The organic concentrate wascarried through the hydrogenation affording 387 g.

Gas chromatographic analysis provided the following analysis (80% totalyield):

isodecanol 25.4%, 98.3 g, 0.621 moles;

isoeicosanol 2.9%, 11.2 g, 0.0380 moles;

tri(isodecyl)cyclopentanes 7.0%, 27.1 g, 0.056 moles (11% yield);

tetra(isodecyl)cyclopentanes 48.1%, 186.1 g, 0.297 moles (56% yield;

penta(isodecyl)cyclopentanes 13.0%, 50.3 g, 0.066 moles (13% yield).

The aqueous layer was acidified with hydrochloric acid and extractedwith ether. The layers were separated and the organic layer washed withwater until neutral. The organics were dried over MgSO₄ and the solventremoved in vacuo, affording isodecanoic acid (23.4 g, 0.136 moles). Ofthe 2.65 moles of isodecanol used, 2.52 moles (95%) are accounted for.

EXAMPLE 4 Hydrogenation of tri(n-decyl)cyclopentadienes

A 4-liter autoclave was charged with the crude alkylcyclopentadienes(159 g; di(n-decyl)cyclopentadienes, 34.7 g, 21.8%;tri(n-decyl)cyclopentadienes, 117.2 g, 73.7%; andtetra(n-decyl)cyclopentadienes 2.2 g, 1.4%), (prepared as in Example 2)10% palladium on activated carbon (4 gms), and heptane (500 ml) tofacilitate stirring. The vessel was pressurized to 500 psi of hydrogenand heated at 125° C. for 19 hours with stirring. After cooling, thevessel pressure was 350 psi. The catalyst was filtered and the solventremoved in vacuo affording 150 g of clear colorless oil with a brominenumber of zero.

EXAMPLE 5

Using the procedures of Examples 1, 2 and 3, the cyclopentadienederivatives set forth in the following Table 1 were prepared. The tableindicates the preparative method used.

                  TABLE 1                                                         ______________________________________                                        CYCLOPENTADIENE DERIVATIVE                                                     ##STR13##                                                                             For-      Meth-   x =                                                R.sub.2    mula    Class.sup.a                                                                           od.sup.b                                                                            2   3   4   5   6                            ______________________________________                                        n-butyl    C.sub.4 H.sub.9                                                                       1°                                                                             P     X   X   X   X   X                            n-hexyl    C.sub.6 H.sub.13                                                                      1°                                                                             P     X   X   X   X   X                            n-octyl    C.sub.8 H.sub.17                                                                      1°                                                                             P, A  X   X   X   X                                n-decyl    C.sub.10 H.sub.21                                                                     1°                                                                             P, A  X   X   X   X                                n-dodecyl  C.sub.12 H.sub.25                                                                     1°                                                                             P, A  X   X   X   X                                n-tetradecyl                                                                             C.sub.14 H.sub.29                                                                     1°                                                                             P     X   X   X                                    isodecyl   C.sub.10 H.sub.21                                                                     1°                                                                             A     X   X   X   X                                isotridecyl                                                                              C.sub.13 H.sub.27                                                                     1°                                                                             A     X   X   X   X                                2-ethyl-1-hexyl                                                                          C.sub.8 H.sub.17                                                                      1°                                                                             P, A  X   X   X                                    2-octyl-1-dodecyl                                                                        C.sub.20 H.sub.41                                                                     1°                                                                             A     X   X                                        2-decyl-1- C.sub.24 H.sub.49                                                                     1°                                                                             A     X   X                                        tetradecyl                                                                    2-octyl    C.sub.8 H.sub.17                                                                      2°                                                                             P, A  X   X                                        t-butyl    C.sub.4 H.sub.9                                                                       3°                                                                             P     X   X                                        ______________________________________                                         .sup.a 1° = primary alkyl; 2° = secondary alkyl; 3°      tertiary alkyl                                                                .sup.b P = Phase Transfer method; A = Alcohol method                     

EXAMPLE 6

Using the procedures of Examples 1, 2 and 3, the methylcyclopentadienesset forth in the following Table 2 were prepared. The preparative methodis indicated.

                  TABLE 2                                                         ______________________________________                                        METHYLCYCLOPENTADIENE                                                          ##STR14##                                                                                          x =                                                     R.sub.2  Formula   Class.sup.a                                                                           Method.sup.b                                                                         2   3    4   5                              ______________________________________                                        n-octyl  C.sub.8 H.sub.17                                                                        1°                                                                             A      X   X    X                                  n-decyl  C.sub.10 H.sub.21                                                                       1°                                                                             A, P   X   X    X                                  n-dodecyl                                                                              C.sub.12 H.sub.25                                                                       1°                                                                             A      X   X    X                                  isodecyl C.sub.10 H.sub.21                                                                       1°                                                                             A      X   X    X                                  ______________________________________                                         .sup.a 1° = primary alkyl                                              .sup.b P = Primary Transfer method; A = Alcohol method                   

EXAMPLE 7

Using the hydrogenation procedures of Example 4, the alkyl substitutedcyclopentanes of Table 3 were prepared. The column indicating "Class"designates a straight or branch chained substituent.

                  TABLE 3                                                         ______________________________________                                        CYCLOPENTANE DERIVATIVES                                                       ##STR15##                                                                                          x =                                                     R.sub.2      Formula  Class.sup.a                                                                             2   3    4   5                                ______________________________________                                        n-octyl      C.sub.8 H.sub.17                                                                       1° X   X    X   X                                n-decyl      C.sub.10 H.sub.21                                                                      1° X   X    X   X                                n-dodecyl    C.sub.12 H.sub.25                                                                      1° X   X    X   X                                isodecyl     C.sub.10 H.sub.21                                                                      1° X   X    X   X                                isotridecyl  C.sub.13 H.sub.27                                                                      1° X   X    X   X                                2-ethyl-1-hexyl                                                                            C.sub.8 H.sub.17                                                                       1° X   X    X                                    2-octyl-1-dodecyl                                                                          C.sub.20 H.sub.41                                                                      1° X   X                                         2-decyl-1-tetradecyl                                                                       C.sub.24 H.sub.49                                                                      1° X   X                                         2-octyl      C.sub.8 H.sub.17                                                                       2° X   X                                         ______________________________________                                         .sup.a 1° = primary alcohol; 2° = secondary alcohol        

EXAMPLE 8

Using the hydrogenation procedures of Example 4, the substitutedmethylcyclopentanes of Table 4 were prepared. The column indicating"Class" designates a straight or branch chained substituent.

                  TABLE 4                                                         ______________________________________                                        METHYLCYCLOPENTANE DERIVATIVES                                                 ##STR16##                                                                                         x =                                                      R.sub.2   FORMULA     CLASS    2     3   4                                    ______________________________________                                        n-octyl   C.sub.8 H.sub.17                                                                          1°                                                                              X     X   X                                    n-decyl   C.sub.10 H.sub.21                                                                         1°                                                                              X     X   X                                    n-dodecyl C.sub.12 H.sub.25                                                                         1°                                                                              X     X   X                                    isodecyl  C.sub.10 H.sub.21                                                                         1°                                                                              X     X   X                                    ______________________________________                                    

EXAMPLE 9 Chemical Identification

Chemical characterization of alkylcyclopentadienes andalkylcyclopentanes was by infrared spectroscopy (IR), nuclear magneticresonance spectrometry (NMR) and gas chromatography (GC), especially inconjunction with mass spectrometry (GC-MS). A few examples weremeticulously examined and structures of products determined and thenquantitative analysis and further identification was made by analogy tothese carefully characterized samples.

Interpretation of Spectroscopic Data Mass Spectrometry

Alkylcyclopentadienes (see Table 5 following)--A detailed analysis ofn-butyl cyclopentadienes showed that the parent peak was prominentenough to be recognizable. Common fragments were P-43(minus n-propyl),P-57(minus n-butyl), P-98(minus propene and butene), P-99(minus n-propyland n-butene) and 57(n-butyl). Other cyclopentadienes also gave parentpeaks prominent enough to allow assignment to be made on that basisalone.

Alkylcycopentanes--Mass spectra are very similar to other saturatedhydrocarbons except that the parent is C_(n) H_(2n).

Infrared Spectroscopy

Alkylcyclopentanes (See Table 6 following)--The IR spectra areindistinguishable from other saturated hydrocarbons with alkylcomponents; e.g., hydrogenated 1-decene oligomers. Bands are at 2960cm⁻¹, 2850 cm¹ (H-C(sp³) stretch); 1460 cm⁻¹, 1375 cm⁻¹, (H-C(sp³) bend)and 720 cm⁻¹ (--(CH₂)_(x) -- rock, x>4).

Alkylcyclopentadienes (See Table 6)--In addition to the bands found inthe alkylcyclopentanes, bands for unsaturation are found at 3050 cm⁻¹(H-C(sp²) stretch, 1650 and 1620 (C=C stretch), 970 and 890 (H--C(sp²)bend).

Nuclear Magnetic Resonance Spectrometry

Alkylcyclopentanes--Both ¹ H and ¹³ C NMR Spectra are dominated byn-alkyl resonances: (1) ¹ H NMR, CH₃ at 0.9 ppm, CH₂ at 1.3 ppm, CH at1.5; (2) ¹³ C NMR, CH₃ --14.2 ppm, CH₂ 's at 22.8 ppm, 29.7 ppm, 32.0ppm and CH's clustered about 40 ppm.

Alkylcyclopentadienes--In addition to the resonance ofalkylcyclopentanes due to the alkyl groups, unsaturation leads toresonances at 5.80 and 6.20 ppm in the ¹ H spectrum for protons on sp²carbon and 2.35 and 2.8 for allylic and bis-allylic CH₂ 's respectively.Similarly, resonances due to unsaturation are observed in the 150.0 to110.00 ppm region for sp² carbons and 45.0 to 35.0 ppm region forallylic carbons in the ¹³ C spectra of alkylcyclopentadienes.

                                      TABLE 5                                     __________________________________________________________________________    Mass Spectral Data for Alkyl Cyclopentadienes                                 GC - Mass Spec of C.sub.5 (R.sub.2).sub.x H.sub.6-x, R.sub.2 = n-butyl        Retention                                                                            INTENSITY (% OF BASE PEAK)                                               Time*                                                                              P (Parent)                                                                          P-43                                                                              P-56                                                                              P-57                                                                              P-71 P-85 P-88 P-99 57                               X (Minutes)                                                                          M.sup.+                                                                             --C.sub.3 H.sub.7                                                                 --C.sub.4 H.sub.8                                                                 --C.sub.4 H.sub.9                                                                 --C.sub.5 H.sub.11                                                                 --C.sub.6 H.sub.13                                                                 --C.sub.7 H.sub.14                                                                 --C.sub.7 H.sub.14                                                                 C.sub.4 H.sub.9                  __________________________________________________________________________    2 20.4 24     45  0  42  24   95   63   100  40                               3 29.4 18     53 55  18  53   19   40   100  60                               3 29.5 18     33  3  16  62   17   27   100  53                               3 32.1 27    100  2  12  10   42   40   42   24                               4 35.8  9     52  3  10  0     8   29   27   100                              4 36.1 22    100 12  23  2    12   47   50   88                               4 36.5 25    100 10  25  2    12   47   38   86                               4 37.2 17     22 88  18  1     7   47   100  62                               4 37.9 30    100  8  20  3    12   35   42   56                               4 38.3  7    <1  18  100 0     1   <1    3   16                               5 40.8 32     79 23  19  0     5   14   38   100                              5 41.4 45    100 23  19  1     6   27   35   67                               5 42.2  5    <1  26  100 0     0    2    2   17                               6 45.5 100    89 32  30  0     2   10   38   37                               __________________________________________________________________________

                  TABLE 6                                                         ______________________________________                                        Infrared Spectra of Representative Alkylcyclopentadienes                      and Alkylcyclopentanes                                                        Di(n-decyl)cyclopentadienes and                                               Di(n-decyl)cyclopentanes.                                                     Frequency, ˜ν                                                         ##STR17##                                                                                  ##STR18##       Assignment                                      ______________________________________                                        3044   cm.sup.-1                 sp.sup.2 CH stretch                          2960             2960            sp.sup.3 CH stretch                          2850             2850            sp.sup.3 CH stretch                          1653                             c = c stretch                                1622                             c = c stretch                                1560                             c = c stretch                                1465             1465            CH.sub.2 bending                             1375             1375            CH.sub.3 bending                             968                              sp.sup.2 CH bend                             891                              sp.sup.2 CH bend                             721               721            (CH.sub.2).sub.x                                                              x > 4,                                                                        rocking                                      ______________________________________                                    

EXAMPLE 10

To evaluate the alkyl cyclopentanes for lubricating properties, testswere carried out to measure physical properties which are relevant touse as a synthetic lubricant. Set forth in the following Table 7 arespecific gravity values of the indicated cyclopentanes, in Table 8 areset forth refractive index values of the indicated cyclopentanes, inTable 9 are set forth viscometric properties of the indicatedalkylcyclopentanes; in Table 10 are low temperature properties of theindicated alkylcyclopentanes; and set forth in Table 11 are hightemperature properties of the indicated alkylcyclopentanes.

                  TABLE 7                                                         ______________________________________                                        Specific Gravity of Representative Alkylcyclopentanes                          ##STR19##                                                                                  X =                                                             Sample #                                                                              R.sub.1                                                                             R.sub.2   2   3     4     5    S.G.                             ______________________________________                                        1       H     (n-decyl) --  100%  --    --   0.8368                           2       H     (n-octyl) --  13    100%  --   0.8368                           3       H     (n-decyl) --  20%   70%   10%  0.8430                           4       H     (n-decyl) --  --    67%   33%  0.8450                           5       H     (n-dodecyl)                                                                             --  40%   60%   --   0.8509                           ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        Refractive Indexes of Representative Alkylcyclopentanes                        ##STR20##                                                                    Sam-                                                                          ple                 X =                                                       #    R.sub.1  R.sub.2   2   3     4     5    n.sub.D.sup.25°           ______________________________________                                                                                     C.                               1    H        n-octyl   --  100%  --    --   1.4573                           2    H        n-decyl   --  100%  --    --   1.4604                           3    H/Me =   n-decyl   --  100%  --    --   1.4612                                1/1                                                                      4    H        n-octyl   --  --    100%  --   1.4612                           5    Me       n-octyl   --  40%   60%   --   1.4630                           6    H        n-decyl   --  30%   65%    5%  1.4636                           7    H        n-decyl   --  --    67%   33%  1.4654                           8    H        n-dodecyl --  40%   60%        1.4647                           9    H        isodecyl                       1.4672                           ______________________________________                                    

                                      TABLE 9                                     __________________________________________________________________________    Viscometric Properties of Representative Alkylcyclopentanes                    ##STR21##                                                                                                       Viscosity                                                      X =            100° C.                                                                    40° C.                                                                     0° C.                                                                      -40° C.                                                                     Viscosity.sup.c           Sample #                                                                            R.sub.1                                                                            R.sub.2  2   3   4   5  (cSt).sup.a                                                                       (cSt).sup.a                                                                       (cP).sup.b                                                                        (cP).sup.b                                                                         Index                     __________________________________________________________________________    1     H    n-octyl  100%                                                                              --  --  -- 2.18                                                                              6.49         158                       2     H    n-decyl  100%                                                                              --  --  -- 3.03                                                                              10.37        161                       3     H    n-dodecyl                                                                              100%                                                                              --  --  -- 4.13                                                                              15.64        178                       4     H    n-octyl  --  100%                                                                              --  -- 3.68                                                                              15.58                                                                             --    1676                                                                             124                       5     H    n-decyl  --  100%                                                                              --  -- 5.15                                                                              23.99        151                       6     Me   n-decyl  --  100%                                                                              --  -- 5.82                                                                              29.64                                                                               247                                                                              6,886                                                                             143                       7     H/Me =                                                                             n-decyl  --  100%                                                                              --  -- 5.60                                                                              27.82                                                                               242                                                                              5,800                                                                             145                             1/1                                                                     8     H    n-dodecyl                                                                              --  100%                                                                              --  -- 6.99                                                                              35.26        150                       9     H    n-octyl  --  --  100%                                                                              -- 5.99                                                                              33.43                                                                               363                                                                              15,386                                                                            125                       10    H    n-decyl  --  --  100%                                                                              -- 7.99                                                                              46.70                                                                               602                                                                              14,958                                                                            143                       11    H    isodecyl --  --  X   -- 11.68                                                                             119.60                                                                             2,584                                                                            556,000                                                                             83                       12    H    isotridecyl                                                                            --  --  X   -- 20.09                                                                             310.22                                                                            12,700                                                                            solid                                                                               71                       13    H    2-octyldodecyl                                                                          15%                                                                               85%                                                                              --  -- 15.10                                                                             114.97                                                                             1,500                                                                            224,000                                                                            136                       14    H    2-decyltetradecyl                                                                       40%                                                                               60%                                                                              --  -- 16.34                                                                             118.51       148                       15    H    n-dodecyl                                                                              --  --   50%                                                                              50%                                                                              11.91                                                                             83.19        153                       __________________________________________________________________________     .sup.a ASTM D445                                                              .sup.b ASTM D3829                                                             .sup.c ASTM D2270                                                        

                                      TABLE 10                                    __________________________________________________________________________    Low Temperature Properties of Representative Alkylcyclopentanes                ##STR22##                                                                                       X =            MRV.sup.a, cp                                                                       CCS .sup.b, cp                                                                     Pour.sup.c                       Sample #                                                                            R.sub.1                                                                            R.sub.2 2   3   4   5  -30° C.                                                                      -25° C.                                                                     Point, °F.                __________________________________________________________________________    1     H    n-octyl 100%                                                                              --  --  --             -10                             2     H    n-decyl 100%                                                                              --  --  --             +40                             3     H    n-dodecyl                                                                             100%                                                                              --  --  --             +70                             4     H    n-octyl --  100%                                                                              --  --    720                                                                                <500                                                                             .sup. <-70°               5     H    n-decyl --  100%                                                                              --  --             -20                             6     H    n-dodecyl                                                                             --  100%                                                                              --  --             +15                             7     H    n-octyl --  --  100%                                                                              --  3,662                                                                                1,640                                                                            <-55                             8     H    n-decyl --  --  100%                                                                              --  4,498                                                                                2,385                                                                            <-75                             9     H    n-dodecyl                                                                             --   40%                                                                               60%                                                                              --              +5                             10    H    n-decyl --   20%                                                                               70%                                                                              10%                                                                               3,375                                                                                2,263                                                                            <-65                             11    Me   n-octyl --   40%                                                                               60%                                                                              --  2,171                                                                                1,200                                                                            .sup. <-60°               12    Me   n-decyl --   67%                                                                               33%                                                                              --  2,549                                                                                1,850                                                                            .sup. <-50°               13    H    n-decyl --  --   67%                                                                              33%                                                                               5,743                                                                                3,500                                                                            .sup. <-50°               14    Me   n-decyl --  100%                                                                              --  --  2,931                                                                                1,350                                                                            .sup. <-60°               15    H/Me =                                                                             n-decyl --  100%                                                                              --  --  2,681                                                                                1,188                                                                            .sup. <-50°                     1:1                                                                     16    H    2-ethylhexyl                                                                          --   95%                                                                               5% --            <-55                             17    H    2-octyl  15%                                                                               85%                                                                              --  --            <-65                             18    H    isodecyl                                                                              --  --  X   -- 103,000                                                                             >15,000                                                                             -30                             19    H    isotridecyl                                                                           --  --  X   -- 369,000                                                                             solid                                                                               -15                             20    H    2-octyldodecyl                                                                         15%                                                                               85%                                                                              --  --  20,500                                                                              11,700                                                                             60                              __________________________________________________________________________     .sup.a MRV = Borderline pumping test by minirotary viscometer (ASTM D38       29)                                                                           .sup.b CCS = Cold cranking simulator (ASTM D2062)                             .sup.c Pour Point (ASTM D97)                                             

                                      TABLE 11                                    __________________________________________________________________________    High Temperature Properties of Alkylcyclopentanes                              ##STR23##                                                                                              Flash.sup.a                                                                       Fire.sup.b                                                    X =         Point,                                                                            Point,                                                                            Evaporation.sup.c                           Sample #                                                                            R.sub.1                                                                         R.sub.2                                                                             2 3   4  5  °F.                                                                        °F.                                                                        Loss, %                                     __________________________________________________________________________    1     H n-decyl                                                                             --                                                                              100%                                                                              -- -- 500 565 0.5                                         2     H n-decyl                                                                             --                                                                              45% 50%                                                                               5%                                                                              520 580 --                                          3     H n-decyl                                                                             --                                                                              --  67%                                                                              33%                                                                              550 620 --                                          4     H n-dodecyl                                                                           --                                                                              40  60%                                                                              -- 560 625 0.1                                         __________________________________________________________________________     .sup.a ASTM D92                                                               .sup.b ASTM D92                                                               .sup.c ASTM D972, 400° F., 6.5 hr., 2L/min N.sub.2                

EXAMPLE 11

To evaluate the hydrocarbon substituted cyclopentadienes for lubricatingproperties, tests were carried out to measure physical properties whichare relevant to use as a synthetic lubricant. Set forth in the followingTable 12 are viscosity and pour point properties of the indicated alkylsubstituted cyclopentadienes. In the cyclopentadienes tested, R₁ ishydrogen, x is 2 to 6 and R₂ is as indicated.

                  TABLE 12                                                        ______________________________________                                        Viscometric Properties of Alkylcyclopentadienes                                                  Vis      Vis    Vis-  Pour.sup.c                                              (100° C.)                                                                       (40° C.)                                                                      cosity.sup.b                                                                        Point,                               Sample                                                                              R.sub.2 ═                                                                              cSt.sup.a                                                                              cSt.sup.a                                                                            Index °F.                           ______________________________________                                        1     n-Butyl      2.65     12.69  -3    <-60                                 2     n-Decyl      5.00     22.35  157      0                                 3     n-octyl/n-decyl                                                                            6.06     31.04  146     -5                                 4     2-octyl-1-dodecyl                                                                          12.78    93.38  133    -50                                 ______________________________________                                         .sup.a - ASTM D445                                                            .sup.b - ASTM D2270                                                           .sup.c - ASTM D97                                                        

The invention has been described herein with reference to certainpreferred embodiments. However, as obvious variations thereon willbecome apparent to those skilled in the art, the invention is not to beconsidered as limited thereto.

What is claimed is:
 1. A cyclopentane of the following formula:##STR24## wherein each R₁ is individually and independently selectedfrom alkyl groups of from 1 to 4 carbon atoms, each R₂ is individuallyand independently selected from C₈ -C₃₆ straight or branch chainedhydrocarbyl groups, z is 0, 1, 2 or 3, and y is an integer ranging from3 to
 6. 2. A cyclopentane according to claim 1 wherein y is
 4. 3. Acyclopentane according to claim 1 wherein Z is 0, each R₂ isindividually selected from C₁₂ to C₂₄ alkyl groups, and y is 3, 4 or 5.4. A cyclopentane according to claim 1 wherein z is 0 or 1, R₁ ismethyl, each R₂ is individually and independently selected from C₈ toC₁₃ alkyl groups and y is 3, 4 or
 5. 5. A mixture of at least twocyclopentanes as defined in claim 1 wherein each R₂ substituent isindividually and independently selected from hydrocarbyl groups ofdifferent carbon chain lengths.
 6. A cyclopentane according to claim 1selected from the group consisting of:Tri-n-octyl cyclopentaneTetra-n-octyl cyclopentane Penta-n-octyl cyclopentane Tri-n-nonylcyclopentane Tetra-n-nonyl cyclopentane Penta-n-nonyl cyclopentaneTri-n-decyl cyclopentane Tetra-n-decyl cyclopentane Penta-n-decylcyclopentane Tri-n-undecyl cyclopentane Tetra-n-undecyl cyclopentanePenta-n-undecyl cyclopentane Tri-n-dodecyl cyclopentane Tetra-n-dodecylcyclopentane Penta-n-dodecyl cyclopentane Tri-2-ethylhexyl cyclopentaneTetra-2-ethylhexyl cyclopentane Di-n-octyl, n-decyl cyclopentanen-octyl, di-n-decyl cyclopentane Trioctyl, n-decyl cyclopentaneDi-n-octyl, di-n-decyl cyclopentane n-octyl, tri-n-decyl cyclopentaneTri-n-tridecyl cyclopentane Tetra-n-tridecyl cyclopentanePenta-n-tridecyl cyclopentane,and mixtures of any two or more in anyproportion.
 7. A cyclopentane of the following formula: ##STR25##wherein each R₁ is individually and independently selected from alkylgroups of from 1 to 4 carbon atoms, each R₂ is individually andindependently selected from C₈ -C₃₆ straight or branch chained alkylgroups, z is 0, 1, 2 or 3, and y is an integer ranging from 2 to 6,providing that when at least two of the R₂ substituents are alkyl groupsof from 4 to 10 carbon atoms, then y must be at least 3, and y+z cannotbe greater than 6.